Combinations of phenylsulfonylurea herbicides and safeners

ABSTRACT

The invention relates to combinations of sulfonylurea herbicides (A) and their salts 
                         
in which R 2  is H, OH, aliphatic hydrocarbon radical or hydrocarbon-oxy radical, and R 1  is an acyl radical, and the other symbols are as defined in claim 1, and safeners of type (B1) and (B2)
 
                         
in which the symbols are as defined in claim 1.

This application is a Continuation of application Ser. No. 08/556,180,filed on Nov. 9, 1995, now abandoned.

The invention to the technical area of crop protection agents, inparticular active substance/antidote combinations (=activesubstance/safener combinations) which are outstandingly suitable for useto combat competing harmful plants in crops of useful plants.

Some of the newer herbicidal active substances have very good propertieson use and can be used with very low application rates to combat a widespectrum of grassy and broad-leaved weeds.

However, many of the very effective active substances are not entirelycompatible with (i.e. not sufficiently selective in) some important cropplants such as corn, rice or cereals, so that there are narrow limits ontheir use. Thus, in some crops they cannot be used at all or can be usedonly with such low application rates that the desired wide herbicidalactivity on harmful plants is not ensured. Specifically, many herbicidesof formula (A), which is defined hereinafter, cannot be used completelyselectively to combat harmful plants in corn, rice, cereals or someother crops.

Some of our recent experimental work has now shown that crop plants suchas corn, rice, wheat, barley and others can, surprisingly, be protectedfrom unwanted damage by said herbicides when they are applied togetherwith certain compounds which act as herbicide antidotes or safeners.

The invention therefore relates to herbicide/safener combinations, forexample in the form of herbicidal compositions, containing

-   A) at least one herbicidal active substance from the group of    substituted phenylsulfonylureas of the formula (A) and salts thereof

-    in which    -   W is O or S, preferably O,    -   A is a group of the formula CR′R″, in which R′ and R″ are,        independently of one another, H or (C₁–C₄)alkyl,    -   Q is O, S or a group NR⁶,    -   m is 0 or 1,    -   n is 0, 1, 2 or 3,    -   R¹ is H, a hydrocarbon radical or a heterocyclic radical, each        of the two last-mentioned radicals being unsubstituted or        substituted,    -   R² is H, OH or an aliphatic hydrocarbon or hydrocarbon-oxy        radical, each of the two last-mentioned radicals being        unsubstituted or substituted,    -   R³ is an acyl radical,    -   R⁴ is halogen, CN, NO₂, (C₁–C₄)alkyl, (C₁–C₄)-alkoxy,        [(C₁–C₄)alkyl]carbonyl, [(C₁–C₄)-alkoxy]carbonyl, each of the        four last-mentioned radicals being unsubstituted or substituted,    -   R⁵ is H, (C₁–C₅)alkyl or (C₁–C₄)alkoxy,    -   R⁶ is H, (C₁–C₄)alkyl, (C₃–C₄)alkenyl, (C₃–C₄)alkynyl, each of        the three last-mentioned radicals being unsubstituted or        substituted by one or more radicals from the group consisting of        halogen, (C₁–C₄)alkyl, (C₁–C₄)alkoxy and (C₁–C₄)alkylthio, or is        (C₁–C₄)alkoxy or OH,    -   X¹, X² are, independently of on another, H, halogen,        (C₁–C₆)alkyl, (C₂–C₆)alkenyl, (C₂–C₆)alkynyl, (C₃–C₇)cycloalkyl,        (C₁–C₆)alkoxy, (C₂–C₆)alkenyloxy, (C₂–C₆)alkynyloxy,        (C₁–C₆)alkylthio, mono- or di-[(C₁–C₄)alkyl]amino, each of the        ten last-mentioned radicals being unsubstituted or substituted        by one or more radicals from the group consisting of halogen,        (C₁–C₄)alkoxy, (C₁–C₄)haloalkoxy and (C₁–C₄)alkylthio, and    -   Z is CH, N or a group of the formula C—R^(o) in which R^(o) is        halogen, cyano, (C₁–C₃)alkyl, (C₁–C₃)haloalkyl, (C₁–C₃)alkoxy or        (C₁–C₃)haloalkoxy,        and-   B) at least one safener from the group of compounds of the formulae    (B1) and (B2)

-   in which    -   X′ is hydrogen, halogen, (C₁–C₄)alkyl, (C₁–C₄)alkoxy, nitro or        (C₁–C₄)haloalkyl,    -   Z′ is OR⁷, SR⁷ or NR⁷R⁸ or is a saturated or unsaturated 3- to        7-membered heterocycle which has at least one nitrogen atom and        up to 3 hetero atoms, is linked via the nitrogen atom to the        carbonyl group in (B1) or (B2) and is unsubstituted or        substituted by radicals from the group consisting of        (C₁–C₄)alkyl, (C₁–C₄)-alkoxy or optionally substituted phenyl,        preferably a radical of the formula OR⁷, NHR⁸ or N(CH₃)₂, in        particular of the formula OR⁷,    -   R* is a (C₁ or C₂)alkanediyl chain which is unsubstituted or        substituted by one or two (C₁–C₄)alkyl radicals or by        [(C₁–C₃)alkoxy]-carbonyl,    -   R⁷ is hydrogen or an unsubstituted or substituted aliphatic        hydrocarbon radical, preferably having a total of 1 to 18 carbon        atoms,    -   R⁸ is hydrogen, (C₁–C₆)alkyl, (C₁–C₆)alkoxy or optionally        substituted phenyl,    -   n′ is an integer from 1 to 5, preferably 1 to 3,    -   W′ is a divalent heterocyclic radical from the group of        partially unsaturated or heteroaromatic 5-membered heterocycles        having 1 to 3 ring hetero atoms of the type of N and O, the ring        containing at least one nitrogen atom and at most one oxygen        atom, preferably a radical from the group of radicals of the        formulae (W1) to (W4),

-   -   R⁹ is hydrogen, (C₁–C₈)alkyl, (C₁–C₈)haloalkyl,        (C₃–C₁₂)cycloalkyl or optionally substituted phenyl,    -   R¹⁰ is hydrogen, (C₁–C₈)alkyl, (C₁–C₈)haloalkyl,        (C₁–C₄)alkoxy-(C₁–C₄)alkyl, (C₁–C₆)hydroxyalkyl, (C₃–C₁₂)        cycloalkyl or tri-(C₁–C₄)alkylsilyl, and    -   m′ is 0 or 1.

Unless specifically defined otherwise, the following definitions applyto the radicals in the formulae (A), (B1) and (B2) and formulaehereinafter.

The radicals alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino andalkylthio, and the corresponding unsaturated and/or substitutedradicals, can be straight-chain or branched in the carbon framework ineach case. Unless specifically indicated, the lower carbon frameworks,e.g. with 1 to 6 carbon atoms, and in the case of unsaturated groupswith 2 to 6 carbon atoms, are preferred for these radicals. Alkylradicals, including in combined meanings such as alkoxy, haloalkyl etc.,are, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl,pentyls, hexyls such as n-hexyl, i-hexyl and 1,3-dimethylbutyl, heptylssuch as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl; alkenyl andalkynyl radicals have the meaning of the possible unsaturated radicalscorresponding to the alkyl radicals; alkenyl is, for example, allyl,1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-butenyl, 3-butenyl,1-methyl-3-butenyl and 1-methyl-2-butenyl; alkynyl is, for example,propargyl, 2-butynyl, 3-butynyl, 1-methyl-3-butynyl. “(C₁–C₄)alkyl” isthe short way of writing alkyl having 1 to 4 carbon atoms; acorresponding statement applies to other general definitions of radicalswith ranges indicated in brackets for the possible number of carbonatoms.

Halogen is, for example, fluorine, chlorine, bromine or iodine.Haloalkyl, -alkenyl and -alkynyl are alkyl, alkenyl and alkynyl,respectively, partly or completely substituted by halogen, preferably byfluorine, chlorine and/or bromine, in particular by fluorine orchlorine, for example CF₃, CHF₂, CH₂F, CF₃CF₂, CH₂FCHCl, CCl₃, CHCl₂,CH₂CH₂Cl; haloalkoxy is, for example, OCF₃, OCHF₂, OCH₂F, CF₃CF₂O,OCH₂CF₃ and OCH₂CH₂Cl; a corresponding statement applies to haloalkenyland other radicals substituted by halogen.

A hydrocarbon radical is a straight-chain, branched or cyclic andsaturated or unsaturated, aliphatic or aromatic hydrocarbon radical, forexample alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl; inthis connection, aryl is a mono- bi- or polycyclic aromatic system, forexample phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl,pentalenyl, fluorenyl and the like, preferably phenyl; a hydrocarbonradical is preferably alkyl, alkenyl or alkynyl having up to 12 carbonatoms or cycloalkyl having 3, 4, 5, 6 or 7 ring atoms or phenyl; acorresponding statement applies to a hydrocarbon radical in ahydrocarbon-oxy radical.

A heterocyclic radical or ring (heterocyclyl) can be saturated,unsaturated or heteroaromatic; it preferably contains one or more heterounits in the ring, preferably from the group consisting of N, O, S, SO,SO₂; it is preferably an aliphatic heterocyclyl radical having 3 to 7ring atoms or a heteroaromatic radical having 5 or 6 ring atoms andcontains 1, 2 or 3 hetero units. The heterocyclic radical can be, forexample, a heteroaromatic radical or ring (heteroaryl) such as, forexample, a mono-, bi- or polycyclic aromatic system in which at least 1ring contains one or more hetero atoms, for example pyridyl,pyrimidinyl, pyridazinyl, pyrazinyl, thienyl, thiazolyl, oxazolyl,furyl, pyrrolyl, pyrazolyl and imidazolyl, or is a partiallyhydrogenated radical such as oxiranyl, pyrrolidyl, piperidyl,piperazinyl, dioxolanyl, morpholinyl, tetrahydrofuryl. Suitablesubstituents for a substituted heterocyclic radical are the substituentsmentioned hereinafter plus, in addition, oxo. The oxo group may alsooccur on the ring hetero atoms which can exist in various oxidationstates, for example N and S.

Substituted radicals, such as substituted hydrocarbon radicals, forexample substituted alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, orsubstituted heterocyclyl or heteroaryl, are, for example, a substitutedradical derived from the unsubstituted parent structure, where thesubstituents are, for example, one or more, preferably 1, 2 or 3,radicals from the group consisting of halogen, alkoxy, haloalkoxy,alkylthio, hydroxyl, amino, nitro, carboxyl, cyano, azido,alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- anddialkylamino-carbonyl, substituted amino such as acylamino, mono- anddialkylamino, and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl,haloalkylsulfonyl and, in the case of cyclic radicals, also alkyl andhaloalkyl, and the unsaturated aliphatic radicals corresponding to thesaid saturated hydrocarbon-containing radicals, such as alkenyl,alkynyl, alkenyloxy, alkynyloxy etc. In the case of radicals with carbonatoms, those having 1 to 4 carbon atoms, in particular 1 or 2 carbonatoms, are preferred. As a rule, preferred substituents are from thegroup consisting of halogen, for example fluorine and chlorine,(C₁–C₄)alkyl, preferably methyl or ethyl, (C₁–C₄)haloalkyl, preferablytrifluoromethyl, (C₁–C₄)alkoxy, preferably methoxy or ethoxy,(C₁–C₄)haloalkoxy, nitro and cyano. Particularly preferred substituentsin this connection are methyl, methoxy and chlorine.

Mono- or disubstituted amino is a chemically stable radical from thegroup of substituted amino radicals which is, for example, N-substitutedby one or two identical or different radicals from the group consistingof alkyl, alkoxy, acyl and aryl; preferably monoalkylamino,dialkylamino, acylamino, arylamino, N-alkyl-N-arylamino and Nheterocycles; in this connection, alkyl radicals having 1 to 4 carbonatoms are preferred; aryl in this connection is preferably phenyl orsubstituted phenyl; the definition of acyl in this connection is thatindicated hereinafter, preferably (C₁–C₄)alkanoyl. A correspondingstatement applies to substituted hydroxylamino or hydrazino.

Optionally substituted phenyl is preferably phenyl which isunsubstituted or substituted one or more times, preferably up to threetimes, by identical or different radicals from the group consisting ofhalogen, (C₁–C₄)-alkyl, (C₁–C₄)alkoxy, (C₁–C₄)haloalkyl,(C₁–C₄)haloalkoxy and nitro, for example o-, m- and p-tolyl,dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro and-trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- andp-methoxyphenyl.

An acyl radical is the radical of an organic acid, for example theradical of a carboxylic acid and radicals of acids derived therefrom,such as thiocarboxylic acid, optionally N-substituted iminocarboxylicacids, or the radical of carbonic monoesters, optionally N-substitutedcarbamic acid, sulfonic acids, sulfinic acids, phosphonic acids,phosphinic acids. Acyl is, for example, formyl, alkylcarbonyl such as(C₁–C₄alkyl)carbonyl, phenylcarbonyl, where the phenyl ring can besubstituted, for example as shown above for phenyl, or alkyloxycarbonyl,phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl,N-alkyl-1-iminoalkyl and other radicals of organic acids.

The formulae (A), (B1) and (B2) also embrace all the stereoisomers whichhave the same topological linkage of the atoms, and mixtures thereof.Such compounds contain one or more asymmetric carbon atoms or elsedouble bonds which are not specially indicated in the general formulae.The possible stereoisomers defined by their specific spatial shape, suchas enantiomers, diastereomers, Z and E isomers, can be obtained bycustomary methods from mixtures of stereoisomers or else be prepared bystereoselective reactions in combination with the use ofstereochemically pure starting materials.

Compounds of the formula (A) are able to form salts in which thehydrogen of the —SO₂—NH— group is replaced by an agriculturally suitablecation. These salts are, for example, metal salts, in particular alkalimetal salts or alkaline earth metal salts, especially sodium andpotassium salts, or else ammonium salts or salts with organic amines.

Compounds of the formula (B1) are disclosed in EP-A-333 131(ZA-89/1960), EP-A-269 806 (U.S. Pat. No. 4,891,057), EP-A-346 620(AU-A-89/34951), EP-A-174 562, EP-A-346 620 and the International PatentApplications PCT/EP 90/01966 (WO-91/08202) and PCT/EP 90/02020(WO-91/07874), and German Patent Application P 43 31 448.1 (WO 95/07897or ZA 94/7120) and literature cited therein or can be prepared byprocesses described therein or analogous ones. Compounds of the formula(B2) are disclosed in EP-A-86 750, EP-A-94 349 (U.S. Pat. No.4,902,340), EP-A-191 736 (U.S. Pat. No. 4,881,966) and EP-A-0 492 366and literature cited therein or can be prepared by the processesdescribed therein or analogous ones. Some compounds are furthermoredescribed in EP-A-0 582 198.

Suitable herbicidal substances according to the invention are thosepyrimidine or triazine derivatives of the formula (A) which cannot, orcannot optimally, be used alone in cereals crops and/or corn becausethey damage the crop plants too much.

Compounds of the formula (A) are disclosed, for example, inWO-A-94/06778, German Patent Applications P 43 35 297.9 (PCT/EP94/03369, WO 95/10507), P 44 15 049.0 and P 44 19 259.2, andWO-A-94/10154 (U.S. Pat. No. 5,449,812) or can be prepared by processesanalogous to those mentioned therein.

Herbicide/safener combinations according to the invention are ofparticular interest when in the safeners (B1) or (B2)

-   R⁷ is hydrogen, (C₁–C₁₈)alkyl, (C₃–C₁₂)cycloalkyl, (C₂–C₈)alkenyl or    (C₂–C₈)alkynyl, where the above C-containing radicals are    unsubstituted or substituted one or more times, preferably up to    three times, by identical or different radicals from the group    consisting of halogen, hydroxyl, (C₁–C₈)alkoxy,    (C₁–C₈)alkylmercapto, (C₂–C₈)alkenylmercapto,    (C₂–C₈)alkynylmercapto, (C₂–C₈)alkynyloxy, (C₂–C₈)alkynyloxy,    (C₃–C₇)cycloalkyl, (C₃–C₇)cycloalkoxy, cyano, mono- and    di-(C₁–C₄-alkyl)amino, carboxyl, (C₁–C₈)alkoxycarbonyl,    (C₂–C₈)alkenyloxycarbonyl, (C₁–C₈)alkylmercaptocarbonyl,    (C₂–C₈)alkynyloxycarbonyl, (C₁–C₈)alkylcarbonyl,    (C₂–C₈)alkenylcarbonyl, (C₂–C₈)alkynylcarbonyl,    1-(hydroxyimino)-(C₁–C₆)alkyl, 1-[(C₁–C₄)alkylimino]-(C₁–C₄)alkyl,    1-[(C₁–C₄)alkoxyimino]-C₁–C₆)alkyl, (C₁–C₈)alkylcarbonylamino,    (C₂–C₈)alkenylcarbonylamino, (C₂–C₈)alkynylcarbonylamino,    aminocarbonyl, (C₁–C₈)alkylaminocarbonyl,    di-(C₁–C₆)alkylaminocarbonyl, (C₂–C₆)alkenylaminocarbonyl,    (C₂–C₆)alkynylaminocarbonyl, (C₁–C₈)alkoxycarbonylamino,    (C₁–C₈)alkylaminocarbonylamino, (C₁–C₆)alkylcarbonyloxy, which is    unsubstituted or substituted by halogen, nitro, (C₁–C₄)alkoxy or    optionally substituted phenyl, or is (C₂–C₆)alkenylcarbonyloxy,    (C₂–C₆)alkynylcarbonyloxy, (C₁–C₈)alkylsulfonyl, phenyl,    phenyl-(C₁–C₆)alkoxy, phenyl-(C₁–C₆)alkoxycarbonyl, phenoxy,    phenoxy-(C₁–C₆)alkoxy, phenoxy-(C₁–C₆)alkoxycarbonyl,    phenylcarbonyloxy, phenylcarbonylamino,    phenyl-(C₁–C₆)alkylcarbonylamino, where the 9 last-mentioned    radicals are unsubstituted or substituted one or more times,    preferably up to three times, in the phenyl ring by identical or    different radicals from the group consisting of halogen,    (C₁–C₄)alkyl, (C₁–C₄)alkoxy, (C₁–C₄)haloalkyl, (C₁–C₄)haloalkoxy and    nitro, and radicals of the formulae —SiR′₃, —O—SiR′₃,    R′₃Si—(C₁–C₈)alkoxy, —CO—O—NR′₂, —O—N═CR′₂, —N═CR′₂, —O—NR′₂, —NR′₂,    CH(OR′)₂, —O—(CH₂)_(m)—CH(OR′)₂, —CR′″(OR′)₂ and    —O—(CH₂)_(m)CR′″(OR″)₂, in which the R′ in the said formulae are,    independently of one another, hydrogen, (C₁–C₄)alkyl, phenyl which    is unsubstituted or substituted one or more times, preferably up to    three times, by identical or diff rent radicals from the group    consisting of halogen, (C₁–C₄)alkyl, (C₁–C₄)alkoxy,    (C₁–C₄)haloalkyl, (C₁–C₄)haloalkoxy and nitro, or pairwise are a    (C₂–C₆)alkanediyl chain and m=0 to 6, and R′″ is hydrogen or    (C₁–C₄)alkyl, and a substituted alkoxy radical of the formula    R″O—CHR′″CH(OR″)—(C₁–C₆)alkoxy, in which the R″ are, independently    of one another, (C₁–C₄)alkyl or together are (C₁–C₆)alkanediyl and    R′″ is hydrogen or (C₁–C₄)alkyl.

Particularly interesting herbicide/safener combinations according to theinvention are also those in which, in the safeners of the formula (B1)or (B2),

-   R⁷ is hydrogen, (C₁–C₈)alkyl or (C₃–C₇)cycloalkyl, where the above    C-containing radicals are unsubstituted or substituted one or more    times by halogen or once or twice, preferably up to once, by    radicals from the group consisting of hydroxyl, (C₁–C₄)alkoxy,    carboxyl, (C₁–C₄)alkoxycarbonyl, (C₂–C₆)alkenyloxycarbonyl,    (C₂–C₆)alkynyloxycarbonyl, 1-(hydroxyimino)-(C₁–C₄)alkyl,    1-[(C₁–C₄)alkylimino]-(C₁–C₄)alkyl,    1-[(C₁–C₄)alkoxyimino]-(C₁–C₄)alkyl and radicals of the formulae    —SiR′₃, —O—N═CR′₂, —N═CR′₂, —NR′₂ and —O—NR′₂, in which the R′ in    the said formulae are, independently of one another, hydrogen or    (C₁–C₄)alkyl or pairwise are a (C₄–C₅)alkanediyl chain,-   R⁹ is hydrogen, (C₁–C₈)alkyl, (C₁–C₆)haloalkyl, (C₃–C₇)cycloalkyl or    phenyl, which is unsubstituted or substituted by one or more of the    radicals from the group consisting of halogen, cyano, nitro, amino,    mono- and di-[(C₁–C₄)alkyl]amino, (C₁–C₄)alkyl, (C₁–C₄)haloalkyl,    (C₁–C₄)alkoxy, (C₁–C₄)haloalkoxy, (C₁–C₄)alkylthio and    (C₁–C₄)alkylsulfonyl, and-   R¹⁰ is hydrogen, (C₁–C₈)alkyl, (C₁–C₈)haloalkyl,    (C₁–C₄-alkoxy)-(C₁–C₄)alkyl, (C₁–C₆)hydroxyalkyl, (C₃–C₇)cycloalkyl    or tri(C₁–C₄)alkylsilyl. and/or-   X′ is hydrogen, halogen, methyl, ethyl, methoxy, ethoxy, (C₁ or    C₂)haloalkyl, preferably hydrogen, halogen or (C₁ or C₂)haloalkyl.

Safeners preferred in this connection are those in which, in formula(B1),

-   X′ is hydrogen, halogen, nitro or (C₁–C₄)haloalkyl,-   n′ is 1, 2 or 3,-   Z′ is a radical of the formula OR⁷,-   R⁷ is hydrogen, (C₁–C₈)alkyl or (C₃–C₇)cycloalkyl, where the above    C-containing radicals are unsubstituted or substituted one or more    times, preferably up to three times, by identical or different    halogen radicals or up to twice, preferably up to once, by identical    or different radicals from the group consisting of hydroxyl,    (C₁–C₄)alkoxy, (C₁–C₄)alkoxycarbonyl, (C₂–C₆)alkenyloxycarbonyl,    (C₂–C₆)alkynyloxycarbonyl, 1-(hydroxyimino)-(C₁–C₄)alkyl,    1-[(C₁–C₄)alkylimino]-(C₁–C₄)alkyl,    1-[(C₁–C₄)alkoxyimino]-(C₁–C₄)alkyl and radicals of the formulae    —SiR′₃, —O—N═R′₂, —N═CR′₂, —NR′₂ and —O—NR′₂, where the radicals R′    in the said formulae are, independently of one another, hydrogen or    (C₁–C₄)alkyl or pairwise are (C₄ or C₅)alkanediyl,-   R⁹ is hydrogen, (C₁–C₈)alkyl, (C₁–C₆)haloalkyl, (C₃–C₇)cycloalkyl or    phenyl, which is unsubstituted or substituted by one or more    radicals from the group consisting of halogen, (C₁–C₄)alkyl,    (C₁–C₄)alkoxy, nitro, (C₁–C₄)haloalkyl and (C₁–C₄)haloalkoxy, and-   R¹⁰ is hydrogen, (C₁–C₈)alkyl, (C₁–C₈)haloalkyl,    (C₁–C₄)alkoxy)-(C₁–C₄)alkyl, (C₁–C₆)hydroxyalkyl, (C₃–C₇)cycloalkyl    or tri(C₁–C₄)alkylsilyl.

Preferred safeners in this connection are also those in which, informula (B2),

-   X′ is hydrogen, halogen or (C₁–C₄)haloalkyl,-   n′ is 1, 2 or 3, where (X′)_(n), is preferably 5-Cl,-   Z′ is a radical of the formula OR⁷,-   R* is CH₂, and-   R⁷ is hydrogen, (C₁–C₈)alkyl, (C₁–C₈)haloalkyl or    (C₁–C₄)alkoxy-(C₁–C₄)alkyl, preferably (C₁–C₈)alkyl.

Particularly preferred safeners in this connection are those in which,in formula (B1),

-   W′ is (W1),-   X′ is hydrogen, halogen or (C₁–C₂)haloalkyl,-   n′ is 1, 2 or 3, where (X′)_(n), is preferably 2,4-Cl₂,-   Z′ is a radical of the formula OR⁷,-   R⁷ is hydrogen, (C₁–C₈)alkyl, (C₁–C₄)haloalkyl, (C₁–C₄)hydroxyalkyl,    (C₃–C₇)cycloalkyl, (C₁–C₄)alkoxy-(C₁–C₄)alkyl,    tri-(C₁–C₂)alkylsilyl, preferably (C₁–C₄)alkyl,-   R⁹ is hydrogen, (C₁–C₈)alkyl, (C₁–C₄)haloalkyl or (C₃–C₇)cycloalkyl,    preferably hydrogen or (C₁–C₄)alkyl, and-   R¹⁰ is hydrogen, (C₁–C₈)alkyl, (C₁–C₄)haloalkyl,    (C₁–C₄)hydroxyalkyl, (C₃–C₇)cycloalkyl, (C₁–C₄)alkoxy-(C₁–C₄)alkyl    or tri-(C₁–C₂)alkylsilyl, preferably hydrogen or (C₁–C₄)alkyl.

Also particularly preferred are herbicidal compositions in which, informula (B1)

-   W′ is (W2),-   X′ is hydrogen, halogen or (C₁–C₂)haloalkyl,-   n′ is 1, 2 or 3, where (X′)_(n), is preferably 2,4-Cl₂,-   Z′ is a radical of the formula OR⁷,-   R⁷ is hydrogen, (C₁–C₈)alkyl, (C₁–C₄)haloalkyl, (C₁–C₄)hydroxyalkyl,    (C₃–C₇)cycloalkyl, (C₁–C₄-alkoxy)-C₁–C₄-alkyl,    tri-(C₁–C₂)alkylsilyl, preferably (C₁–C₄)alkyl, and-   R⁹ is hydrogen, (C₁–C₈)alkyl, (C₁–C₄)haloalkyl, (C₃–C₇)cycloalkyl or    phenyl, preferably hydrogen or (C₁–C₄)alkyl.

Also particularly preferred in this connection are safeners in which, informula (B1),

-   W′ is (W3),-   X′ is hydrogen, halogen or (C₁–C₂)haloalkyl,-   n′ is 1, 2 or 3, where (X′)_(n), is preferably 2-4-Cl₂,-   Z′ is a radical of the formula OR⁷,-   R⁷ is hydrogen, (C₁–C₈)alkyl, (C₁–C₄)haloalkyl, (C₁–C₄)hydroxyalkyl,    (C₃–C₇)cycloalkyl, (C₁–C₄)alkoxy-(C₁–C₄)alkyl,    tri-(C₁–C₂)alkylsilyl, preferably (C₁–C₄)alkyl, and-   R⁹ is (C₁–C₈)alkyl or (C₁–C₄)haloalkyl, preferably C₁-haloalkyl.

Also particularly preferred in this connection are safeners in which, informula (B1),

-   W′ is (W4),-   X′ is hydrogen, halogen, nitro, (C₁–C₄)alkyl or (C₁–C₂)haloalkyl,    preferably CF₃, or (C₁–C₄)alkoxy,-   n′ is 1, 2 or 3,-   m′ is 0 or 1,-   Z′ is a radical of the formula OR⁷, and-   R⁷ is hydrogen, (C₁–C₄)alkyl, carboxy-(C₁–C₄)alkyl or    (C₁–C₄)alkoxycarbonyl-(C₁–C₄)alkyl, preferably    (C₁–C₄)alkoxy-CO—CH₂—, (C₁–C₄)alkoxy-CO—C(CH₃)H—, HO—CO—CH₂— or    HO—CO—C(CH₃)H— and-   R⁹ is H, (C₁–C₄)alkyl, (C₁–C₄)haloalkyl, (C₃–C₇)cycloalkyl or phenyl    which is unsubstituted or substituted by one or more radicals from    the group consisting of halogen, (C₁–C₄)alkyl, (C₁–C₄)haloalkyl,    nitro, cyano and (C₁–C₄)alkoxy.

The following groups of compounds are suitable examples of safeners forthe abovementioned herbicidal active substances (A):

-   a) compounds of the dichlorophenylpyrazoline-3-carboxylic acid type    (i.e. of the formula (B1) in which W′=W1 and (X′)_(n′)=2,4-Cl₂),    preferably compounds such as ethyl    1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate    (B1-1) and related compounds as described in WO 91/07874,-   b) derivatives of dichlorophenylpyrazolecarboxylic acid (i.e. of the    formula (B1) in which W′=W2 and (X′)_(n′)=2,4-Cl₂), preferably    compounds such as ethyl    1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (B1-2), ethyl    1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (B1-3),    thyl    1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate    (B1-4), ethyl 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate    (B1-5) and related compounds as described in EP-A-333 131 and    EP-A-269 806.-   c) Compounds of the triazolecarboxylic acid type (i.e. of the    formula (B1), in which W′=W3 and (X′)_(n′)=2,4-Cl₂), preferably    compounds such as fenchlorazole, i.e. ethyl    1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylate    (B1-6) and related compounds (see EP-A-174 562 and EP-A-346 620);-   d) Compounds of the type of 5-benzyl- or    5-phenyl-2-isoxazoline-3-carboxylic acid or of    5,5-diphenyl-2-isoxazoline-3-carboxylic acid, preferably compounds    such as ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate    (B1-7) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (B1-8) and    related compounds as described in WO 91/08202, and ethyl (B1-9) or    n-propyl (B1-10) 5,5-diphenyl-2-isoxazolinecarboxylate or ethyl    5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (B1-11), as    described in German Patent Application P 43 31 448.1    (WO-A-95/07897).-   e) Compounds of the 8-quinolinoxyacetic acid type, for example those    of the formula (B2) in which (X′)_(n′)=5-Cl, hydrogen, Z′=OR⁷,    R*=CH₂, preferably compounds such as 1-methylhexyl    (5-chloro-8-quinolinoxy)acetate (B2-1), 1,3-dimethylbutyl    (5-chloro-8-quinolinoxy)acetate (B2-2), 4-allyloxybutyl    (5-chloro-8-quinolinoxy)acetate (B2-3), 1-allyloxy-2-propyl    (5-chloro-8-quinolinoxy)acetate (B2-4), ethyl    (5-chloro-8-quinolinoxy)acetate (B2-5), methyl    (5-chloro-8-quinolinoxy)acetate (B2-6), allyl    (5-chloro-8-quinolinoxy)acetate (B2-7),    2-(2-propylideneiminoxy)ethyl (5-chloro-8-quinolinoxy)acetate    (B2-8), 2-oxopropyl (5-chloro-8-quinolinoxy)acetate (B2-9) and    related compounds as described in EP-A-86 750, EP-A-94 349 and    EP-A-191 736 or EP-A-0 492 366.-   f) Compounds of the (5-chloro-8-quinolinoxy)malonic acid type (i.e.    of the formula (B2) in which (X′)_(n′)=5-Cl, Z′=OR⁷,    R*=—CH(COO-alkyl)), preferably compounds such as diethyl    (5-chloro-8-quinolinoxy)malonate, diallyl    (5-chloro-8-quinolinoxy)malonate, methyl ethyl    (5-chloro-8-quinolinoxy)malonate and related compounds as described    in EP-A-0 582 198.-   g) Active substances of the type of phenoxyacetic or -propionic acid    derivatives or of aromatic carboxylic acids such as, for example,    2,4-dichlorophenoxyacetic acid (ester) (2,4-D),    4-chloro-2-methylphenoxypropionic ester (mecoprop), MCPA or    3,6-dichloro-2-methoxybenzoic acid (ester) (dicamba).

Particularly interesting herbicides/safener combinations according tothe invention are those in which, in compounds of the formula (A) ortheir salts,

-   R¹ is an aliphatic hydrocarbon radical which has up to 24 carbon    atoms and which is unsubstituted or substituted, preferably    (C₁–C₆)alkyl, (C₂–C₆)alkenyl, (C₂–C₆)alkynyl, (C₃–C₆)cycloalkyl,    each of the four last-mentioned radicals being unsubstituted or    substituted by one or more radicals from the group consisting of    halogen, CN, (C₁–C₄)alkoxy, (C₁–C₄)alkylthio, (C₁–C₄) haloalkoxy,    mono-(C₁–C₄alkyl)amino, di-(C₁–C₄alkyl)amino, (C₁–C₄)alkylsulfonyl,    (C₁–C₄-alkyl)aminocarbonyl, di(C₁–C₄alkyl)aminocarbonyl, phenyl and    substituted phenyl, or a radical of the type heterocyclyl or    heterocyclyl-(C₁–C₄)alkyl having 3 to 7 ring atoms, preferably a    radical of formulae A-1 to A-13

-   X is O, S, S(O) or SO₂, preferable O,-   R² is H, OH, an aliphatic hydrocarbon radical or hydrocarbon-oxy    radical which is unsubstituted or substituted and contains a total    of up to 18, preferably up to 12, in particular up to 8, carbon    atoms, preferably H, OH, (C₁–C₆)alkyl, (C₃–C₇)cycloalkyl,    (C₂–C₆)alkenyl, (C₂–C₆)alkynyl, (C₁–C₆)alkoxy, (C₃–C₇)cycloalkoxy,    (C₂–C₆)alkenyloxy, (C₂–C₆)alkynyloxy, the eight last-mentioned    radicals being unsubstituted or substituted by one or more radicals    from the group consisting of (C₁–C₄)alkoxy, (C₁–C₄)haloalkoxy,    (C₂–C₄)alkenyloxy, (C₂–C₄)haloalkenyloxy, (C₂–C₄)alkynyloxy,    (C₂–C₄)haloalkynyloxy, (C₁–C₄)alkylthio, (C₁–C₄)haloalkylthio,    halogen, OH, NH₂, mono- and di[(C₁–C₄)alkyl]amino, CN, NO₂, CONH₂,    CHO, [(C₁–C₆)alkyl]carbonyl, (C₁–C₄)alkylsulfonyl,    [(C₁–C₄)alkoxy]carbonyl, mono- and di-[(C₁–C₄)alkyl]-aminocarbonyl,    and in the case of cyclic radicals also (C₁–C₄)alkyl and    (C₁–C₄)haloalkyl,-   R³ is CO—R¹¹, CO—OR¹², CO—NR¹³R¹⁴, CO—SR¹⁵, CS—R¹⁶, CS—OR¹⁷,    CS—NR¹⁸R¹⁹, CS—SR²⁰, SO₂R²¹, SO₂NR²²R²³,-   R¹¹ is H, (C₁–C₆)alkyl, (C₂–C₆)alkenyl, (C₂–C₆)alkynyl, the three    last-mentioned radicals being, independently of one another,    unsubstituted or substituted by one or more radicals from the group    consisting of halogen, (C₁–C₄)alkoxy, (C₁–C₄)alkylthio and NR²⁴R²⁵,    or unsubstituted or substituted (C₃–C₈)cycloalkyl, unsubstituted or    substituted phenyl, unsubstituted or substituted heteroaryl or    phenyl-(C₁–C₄)alkyl which is unsubstituted or substituted on the    phenyl ring,-   R¹² is (C₁–C₆)alkyl, (C₂–C₆)alkenyl, (C₂–C₆)alkynyl, the three    last-mentioned radicals being, independently of one another,    unsubstituted or substituted by one or more radicals from the group    consisting of halogen, (C₁–C₄)alkoxy, (C₁–C₄)alkylthio and NR²⁶R²⁷,    or, (C₃–C₆)cycloalkyl which is unsubstituted or substituted by one    or more radicals from the group consisting of halogen, (C₁–C₄)alkyl    and (C₁–C₄)alkoxy, or (C₃–C₆)cycloalkyl-(C₁–C₃)alkyl,-   R¹³ is H, (C₁–C₆)alkyl, (C₂–C₆)alkenyl, (C₂–C₆)alkynyl, the three    last-mentioned radicals being, independently of one another,    unsubstituted or substituted by one or more radicals from the    halogen group, or is [(C₁–C₆)alkoxy]carbonyl, (C₁–C₄)alkoxy or OH,-   R¹⁴ is H, (C₁–C₆)alkyl, (C₂–C₆)alkenyl, (C₂–C₆)alkynyl, the three    last-mentioned radicals being, independently of one another,    unsubstituted or substituted by one or more radicals from the group    consisting of halogen, (C₁–C₄)alkoxy, (C₁–C₄)alkylthio and NR²⁸R²⁹-   or NR¹³R¹⁴ is a heterocyclic radical which, besides the nitrogen    atom, can contain further hetero units from the group consisting of    O, N, S, SO or SO₂ in the ring framework and which is unsubstituted    or substituted by one or more radicals from the group consisting of    halogen, OH, NH₂, NHCH₃, N(CH₃)₂, CN, CONHCH₃, CO₂CH₃, COCH₃,    CON(CH₃)₂, CHO, (C₁–C₃)alkyl, CONH₂, (C₁–C₃)alkoxy,    (C₁–C₃)haloalkoxy, (C₁–C₃)haloalkyl and the oxo group,-   R¹⁵ is a radical analogous to R¹²,-   R¹⁶ is a radical analogous to R¹¹,-   R¹⁷ is a radical analogous to R¹²,-   R¹⁸ is a radical analogous to R¹³,-   R¹⁹ is a radical analogous to R¹⁴,-   or NR¹⁸R¹⁹ is a radical analogous to NR¹³R¹⁴,-   R²⁰ is a radical analogous to R¹²,-   R²¹ is (C₁–C₆)alkyl, (C₂–C₆)alkenyl, (C₂–C₆)alkynyl, the three    last-mentioned radicals being, independently of one another,    unsubstituted or substituted by one or more radicals from the group    consisting of halogen, (C₁–C₄)alkoxy, (C₁–C₄)alkylthio and NR³⁰R³¹,-   R²² is a radical analogous to R¹³,-   R²³ is a radical analogous to R¹⁴ or-   NR²²R²³ is a radical analogous to NR¹³R¹⁴,-   R²⁴ is H, (C₁–C₄)alkyl, (C₁–C₄)haloalkyl, (C₁–C₄)alkenyl,    (C₁–C₄)haloalkenyl, (C₁–C₄)alkoxys (C₁–C₄)haloalkoxy or hydroxyl,-   R²⁵ is H, (C₁–C₄)alkyl, (C₁–C₄)haloalkyl, (C₁–C₄)alkenyl or    (C₁–C₄)haloalkenyl,-   R²⁶ is analogous to R²⁴,-   R²⁷ is analogous to R²⁵,-   R²⁸ is analogous to R²⁴,-   R²⁹ is analogous to R²⁵,-   R³⁰ is analogous to R²⁴ and-   R³¹ is analogous to R²⁵.

The term “analogous” in a definition such as “R¹⁵ is a radical analogousto R¹²” means that R¹⁵ and R¹² are identical or different radicals aslisted in the definition of R¹².

Also of particular interest are herbicide/safener combinations accordingto the invention where, in the compounds of the formula (A) and saltsthereof,

-   R¹ is (C₁–C₆)alkyl, (C₂–C₆)alkenyl, (C₂–C₆)alkynyl,    (C₃–C₆)cycloalkyl, each of the four last-mentioned radicals being    unsubstituted or substituted by one or more radicals from the group    consisting of F, Cl, Br, I, CN, OCH₃, OCF₃, N(CH₃)₂, SO₂CH₃, CO₂CH₃,    CO₂N(CH₃)₂ and phenyl, or a group of said formula A-1 to A-13,-   R² is H, (C₁–C₄)alkyl, (C₂–C₄)alkenyl, (C₂–C₄)alkynyl,    (C₃–C₆)cycloalkyl or (C₁–C₄)haloalkyl,-   R³ is CO—R¹¹, CO—OR¹², CO—NR¹³R¹⁴ or SO₂R²¹,-   R⁴ is halogen, (C₁–C₃)alkyl or (C₁–C₃)alkoxy,-   n is 0 or 1,-   m is 0 or 1,-   R⁵ is H or CH₃,-   R¹¹ is H, (C₁–C₆)alkyl, (C₂–C₄)alkenyl, (C₂–C₄)alkynyl,    (C₁–C₄)haloalkyl, (C₁–C₄)alkoxy-(C₁–C₄)alkyl, phenyl or heteroaryl    with 5 or 6 ring atoms, each of the two last-mentioned radicals    being unsubstituted or substituted,-   R¹² is a radical analogous to R¹¹, apart from hydrogen,-   R¹³, R¹⁴ are, independently of one another, H or (C₁–C₄)alkyl,-   R²¹ is (C₁–C₄)alkyl, (C₁–C₄)haloalkyl or (C₁–C₄)alkoxy-(C₁–C₄)alkyl,-   one of the radicals X¹ and X² is halogen, (C₁–C₂)alkyl,    (C₁–C₂)alkoxy, (C₁–C₂)alkylthio, each of the three last-mentioned    radicals being unsubstituted or substituted by one or more radicals    from the group consisting of halogen, (C₁–C₂)alkoxy and    (C₁–C₂)alkylthio, or mono- or di(C₁–C₂-alkyl)amino, preferably    halogen, methyl or methoxy, and-   the other one of the radicals X¹ and X² is (C₁–C₂)alkyl,    (C₁–C₂)haloalkyl, (C₁–C₂)alkoxy, (C₁–C₂)haloalkoxy or    (C₁–C₂)alkylthio, preferably methyl or methoxy,-   Z is CH or N.

Preferred compounds of the formula (I) and salts thereof according tothe invention are those in which

-   R¹ is (C₁–C₄)alkyl, preferably methyl or ethyl,-   R² is H, (C₁–C₄)alkyl, preferably methyl or ethyl,-   R³ is formyl, acetyl, n-propionyl, i-propionyl, 2-methylpropionyl,    n-butanoyl, cyclopropylcarbonyl, methoxycarbonyl, ethoxycarbonyl,    trifluoroacetyl, methylsulfonyl,-   m is 0 or 1,-   n is zero,-   R⁵ is hydrogen,-   A is CH₂,-   Q is an oxygen atom or N(CH₃),-   X¹ is OCH₃, OC₂H₅ or Cl,-   X² is OCH₃ or OC₂H₅,-   Z is CH or N.

The safeners (antidotes) of the formulae (B1) and (B2), for examplesafeners of the abovementioned groups a) to g), reduce or suppressphytotoxic effects which may occur on use of the herbicidal activesubstances of the formula (A) in crops of useful plants, with negligibleimpairment of the activity of these herbicidal active substances onharmful plants. This makes it possible very considerably to extend therange of uses of conventional crop protection agents and extend it, forexample, to crops such as wheat, barley, corn and other graminaceouscrops in which use of the herbicides has hitherto been impossible orpossible to only a limited extent, that is to say in low doses with nota very broad action.

The herbicidal active substances and the safeners mentioned can beapplied together (as ready-to-use formulation or in the tankmix process)or in any desired sequence one after the other. The safener:herbicidalactive substance ratio by weight can vary within wide limits and ispreferably in the range from 1:100 to 100:1, in particular from 1:10 to10:1. The optimal quantities of herbicidal active substance and safenerin each case depend on the type of herbicidal active substance used oron the safener used and on the type of crop to be treated and can bedetermined by appropriate preliminary tests in each case.

The main areas of use of the safeners are, in particular, corn andcereals crops (wheat, rye, barley, oats), rice, sorghum, but also cottonand soybean, preferably cereals and corn.

The safeners of the formulae (B1) and (B2) can, depending on theirproperties, be used for pretreatment of the seed of the crop plant (seeddressing) or be introduced before sowing into the seed furrows orapplied together with the herbicide before or after emergence of theplants. Pre-emergence treatment includes both treatment of the growingarea before sowing and treatment of the growing areas which have beensown but as yet show no growth. Use together with the herbicide ispreferred. Tank mixes or ready-to-use formulations can be used for thispurpose.

The safener application rates required may vary within wide limitsdepending on the indication and herbicidal active substance used andare, as a rule, in the range from 0.001 to 5 kg, preferably 0.005 to 0.5kg, of active substance per hectare.

The present invention therefore also relates to a method for protectingplants from the phytotoxic side effects of herbicides of the formula(A), which comprises applying an effective quantity of a compound of theformula (B1) and/or (B2) before, after or at the same time as theherbicidal active substance of the formula (A) to the plants, plantseeds or the growing area.

The compounds of the formulae (B1) and (B2) and combinations thereofwith one or more of said herbicidal active substances can be formulatedin a variety of ways, depending on the specified biological and/orphysico-chemical parameters. Examples of possible and suitableformulations are: wettable powders (WP), emulsifiable concentrates (EC),water-soluble powders (SP), water-soluble concentrates (SL),concentrated emulsions (BW) such as oil-in-water and water-in-oilemulsions, sprayable solutions or emulsions, capsule suspensions (CS),oil- or water-based dispersions (SC), suspoemulsions, suspensionconcentrates, dustable powders (DP), oil-miscible solutions (OL), seeddressings, granules (GR) in the form of micro-, sprayable, absorptionand adsorption granules, granules for soil application or distribution,water-soluble granules (SG), water-dispersible granules (WG), ULVformulations, microcapsules and waxes.

These individual formulation types are known in principle and aredescribed, for example, in: Winnacker-Küchler, “Chemische Technologie”[Chemical Technology], Volume 7, C. Hauser Verlag, Munich, 4th Edition,1986; Wade van Valkenburg, “Pesticide Formulations”, Marcel Dekker N.Y.,1973; K. Martens, “Spray Drying Handbook”, 3rd Ed. 1979, G. Goodwin Ltd.London.

The formulation auxiliaries required, such as inert materials,surfactants, solvents and other additives are likewise known and aredescribed, for example, in: Watkins, “Handbook of Insecticide DustDiluents and Carriers”, 2nd Ed., Darland Books, Caldwell N.J., H. v.Olphen, “Introduction to Clay Colloid Chemistry”; 2nd Ed., J. Wiley &Sons, N.Y.; C. Marsden, “Solvents Guide”; 2nd Ed., Interscience, N.Y.1963; McCutcheon's “Detergents and Emulsifiers Annual”, MC Publ. Corp.,Ridgewood N.J.; Sisley and Wood, “Encyclopedia of Surface ActiveAgents”, Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt,“Grenzflächenaktive Äithylenoxidaddukte” [Surface-active Ethylene OxideAdducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler,“Chemische Technologie” [Chemical Technology], Volume 7, C. HauserVerlag, Munich, 4th Edition, 1986.

It is also possible on the basis of these formulations to producecombinations with other substances with pesticidal activity, such as,for example, insecticides, acaricides, herbicides, fungicides, and withsafeners, fertilizers and/or growth regulators, for example in the formof a ready-to-use formulation or tankmix.

Wettable powders are products which can be uniformly dispersed in waterand which, besides the active substance and apart from a diluent orinert substance, also contain ionic and/or nonionic surfactants (wettingagents, dispersants), for example polyoxyethylated alkylphenols,polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fattyalcohol polyglycol ether sulfates, alkanesulfonates,alkylbenzenesulfonates, sodium ligninsulfonate, sodium2,2′-dinaphthylmethane-6,6′-disulfonate, sodiumdibutylnaphthalenesulfonate or else oleoylmethyltaurine sodium salt. Thewettable powders are produced by finely milling the herbicidal activesubstances, for example in customary apparatus such-as hammer mills,integral fan mills and air jet mills and mixed, simultaneously orsubsequently, with the formulation auxiliaries.

Emulsifiable concentrates are produced by dissolving the activesubstance in an organic solvent, for example butanol, cyclohexanone,dimethylformamide, xylene or else higher-boiling aromatic compounds orhydrocarbons or mixtures of the organic solvents with the addition ofone or more ionic and/or nonionic surfactants (emulsifiers). Examples ofemulsifiers which can be used are: calcium alkylarylsulfonates such asCa dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acidpolyglycol ethers, alkylaryl polyglycol ethers, fatty alcohol polyglycolethers, propylene oxide/ethylene oxide condensation products, alkylpolyethers, sorbitan esters such as, for example, sorbitan fatty acidesters or polyoxyethylene sorbitan esters such as, for examplepolyoxyethylene sorbitan fatty acid esters.

Dustable powders are obtained by milling the active substance withfinely divided solid substances, for example talc, natural clays such askaolin, bentonit and pyrophyllite, or diatomaceous earth.

Suspension concentrates can be water- or oil-based. They can beproduced, for example, by wet milling using commercially available beadmills and, where appropriate, adding surfactants as have already beenlisted above, for example, for the other types of formulation.

Emulsions, for example oil-in-water emulsions (EW), can be produced, forexample, by means of stirrers, colloid mills and/or static mixers usingaqueous organic solvents and, where appropriate, surfactants as havealready been listed above, for example, for the other types offormulation.

Granules can be produced either by spraying the active substance ontogranulated inert adsorbent material or by applying active substanceconcentrates by means of adhesives, for example polyvinyl alcohol,sodium polyacrylate or else mineral oils, onto the surface of carrierssuch as sand, kaolinites or granulated inert material. It is alsopossible for suitable active substances to be granulated in the waycustomary for producing fertilizer granules—if required mixed withfertilizers.

Water-dispersible granules are, as a rule, produced by customaryprocesses such as spray drying, fluidized bed granulation, plategranulation, mixing with high-speed mixers and extrusion without solidinert material.

On the production of plate, fluidized bed, extruder and spray granules,see, for example, processes in “Spray-Drying Handbook” 3rd Ed., 1979, G.Goodwin Ltd., London; J. E. Browning, “Agglomeration”, Chemical andEngineering 1967, pages 147 et seq.; “Perry's Chemical Engineer'sHandbook”, 5th Ed., McGraw-Hill, New York 1973, pages 8–57.

For further details of the formulation of crop protection agents, see,for example, G. C. Klingman, “Weed Control as a Science”, John Wiley andSons, Inc., New York, 1961, pages 81–96 and J. D. Freyer, S. A. Evans,“Weed Control Handbook”, 5th Ed., Blackwell Scientific Publications,Oxford, 1968, pages 101–103.

The agrochemical compositions contain, as a rule, from 0.1 to 99% byweight, in particular 0.1 to 95% by weight, of active substances of theformula (B1) and/or (B2) or of the herbicide/antidote active substancemixture (A) and (B1) and/or (B2) and 1 to 99.9% by weight, in particular5 to 99.8% by weight, of a solid or liquid additive and 0 to 25% byweight, in particular 0.1 to 25% by weight, of a surfactant.

The active substance concentration in wettable powders is, for example,about 10 to 90% by weight, and the remainder up to 100% by weightconsists of customary formulation ingredients. The active substanceconcentration in emulsifiable concentrates is about 1 to 80% by weight.Formulations in dust form contain about 1 to 20% by weight of activesubstances, and sprayable solutions contain about 0.2 to 20% by weightof active substances. In granules, such as water-dispersible granules,the active substance content partly depends on whether the activecompound is in liquid or solid form. As a rule, the content inwater-dispersible granules is between 10 and 90% by weight.

The said active substance formulations additionally contain whereappropriate the adhesives, wetting agents, dispersants, emulsifiers,penetration promoters, preservatives, frost protection agents andsolvents, fillers, carriers and dyes, antifoam agents, evaporationinhibitors and agents influencing the pH and viscosity which arecustomary in each case.

Examples of active substances which can be used as combination partnersfor the active substances according to the invention in mix formulationsor in a tankmix are those described, for example in Weed Research 26,441–445 (1986), or “The Pesticide Manual”, 9th edition, The British CropProtection Council, 1990/91, Bracknell, England, and literature citedtherein. The following active substances may be mentioned as examples ofherbicides which are disclosed in the literature and can be combinedwith the compounds of the formula (I). (Note: the compounds areidentified either by the “common name” according to the InternationalOrganization for Standardization (ISO) or by the chemical name, whereappropriate together with a conventional code number): acetochlor;acifluorfen; aclonifen; AKH 7088, i.e.[[[1-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl]-2-methoxyethylidene]amino]oxy]aceticacid and -acetic acid methyl ester; alachlor; alloxydim; ametryn;amidsulfuron; amitrol; AMS, i.e. ammonium sulfamate; anilofos; asulam;atrazin; azimsulfurone (DPX-A8947); aziprotryn; barban; BAS 516 H, i.e.5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazolin; benfluralin;benfuresate; bensulfuron-methyl; bensulide; bentazone; benzofenap;benzofluor; benzoylpropethyl; benzthiazuron; bialaphos; bifenox;bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos;busoxinone; butachlor; butamifos; butenachlor; buthidazole; butralin;butylate; caferstrole (CH-900):; carbetamide; carentrazone (ICI-A0051);CDAA, i.e. 2-chloro-N,N-di-2-propenylacetamide; CDEC, i.e. 2-chloroallyldiethyldithiocarbamate; chlomethoxyfen; chloramben; chlorazifop-butyl,chlormesulon (ICI-A0051); chlorbromuron; chlorbufam; chlorfenac;chlorflurecol-methyl; chloridazon; chlorimuron ethyl; chlornitrofen;chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron;chlorthal-dimethyl; chlorthiamid; cinmethylin; cinosulfuron; clethodim;clodinafop and its ester derivatives (for example clodinafop-propargyl);clomazone; clomeprop; cloproxydim; clopyralid; cumyluron, (JC 940);cyanazine; cycloate; cyclosulfamuron (AC 104); cycloxydim; cycluron;cyhalofop and its ester derivatives (for example butyl ster, DEH-112);cyperquat; cyprazine; cyprazole; daimuron; 2,4-DB; dalapon; desmedipham;desmetryn; di-allate; dicamba; dichlobenil; dichlorprop; diclofop andits esters such as diclofop-methyl; diethatyl; difenoxuron; difenzoquat;diflufenican; dimefuron; dimethachlor; dimethametryn; dimethenamid(SAN-582H); dimethazone, clomazon; dimethipin; dimetrasulfuron,dinitramine; dinoseb; dinoterb; diphenamid; dipropetryn; diquat;dithiopyr; diuron; DNOC; eglinazineethyl; EL 177, i.e.5-cyano-1-(1,1-dimethylethyl)-N-methyl-1H-pyrazole-4-carboxamide;endothal; EPTC; esprocarb; ethafluralin; ethametsulfuron-methyl;ethidimuron; ethiozin; ethofumesate; F5231, i.e.N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]phenyl]ethanesulfonamide;ethoxyfen and its esters (for example ethyl ester, HN-252); etobenzanid(HW 52); fenoprop; fenoxan, fenoxaprop and fenoxaprop-P and theiresters, for example fenoxaprop-P ethyl and fenoxaprop-ethyl; fenoxydim;fenuron; flamprop-methyl; flazasulfuron; fluazifop and fluazifop-P andtheir esters, for example fluazifop-butyl and fluazifop-P-butyl;fluchloralin; flumetsulam; flumeturon; flumiclorac and its esters (forexample pentyl ester, S-23031); flumioxazin (S-482); flumipropyn;flupoxam (KNW-739); fluorodifen; fluoroglycofen-ethyl; flupropacil(UBIC-4243); fluridone; flurochloridone; fluroxypyr; flurtamone;fomesafen; fosamine; furyloxyfen; glufosinate; glyphosate; halosaten;halosulfuron and its esters (for example methyl ester, NC-319);haloxyfop and its esters; haloxyfop-P (=R-haloxyfop) and its esters;hexazinone; imazamethabenz-methyl; imazapyr; imazaquin and salts such asthe ammonium salt; imazethamethapyr; imazethapyr; imazosulfuron;ioxynil; isocarbamid; isopropalin; isoproturon; isouron; isoxaben;isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MCPA; MCPB;mecoprop; mefenacet; mefluidid; metamitron; metazachlor;methabenzthiazuron; metham; methazole; methoxyphenone; methyldymron;metabenzuron, methobenzuron; metobromuron; metolachlor; metosulam (XRD511); metoxuron; metribuzin; metsulfuron-methyl; MH; molinat ; monalide;monocarbamide dihydrogensulfate; monolinuron; monuron; MT 128, i.e.6-chloro-N-(3-chloro-2-propenyl)-5-methyl-N-phenyl-3-pyridazinamine; MT5950, i.e. N-[3-chloro-4-(1-methylethyl)phenyl]-2-methylpentanamide;naproanilide; naptalam; NC 310, i.e.4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole; neburon;nicosulfuron; nipyrachlophen; nitralin; nitrofen; nitrofluorfen;norflurazon; orbencarb; oryzalin; oxadiargyl (RP-020630); oxadiazon;oxyfluorfen; paraquat; pebulate; pendimethalin; perfluidone;phenisopham; phenmedipham; picloram; piperophos; piributicarb;pirifenop-butyl; pretilachlor; primisulfuron-methyl; procyazine;prodiamine; profluralin; proglinazine-ethyl; prometon; prometryn;propachlor; propanil; propaquizafop and its esters; propazine; propham;propisochlor; propyzamide; prosulfalin; prosulfocarb; prosulfuron(CGA-152005); prynachlor; pyrazolinate; pyrazon; pyrazosulfuron-ethyl;pyrazoxyfen; pyridate; pyrithiobac (KIH-2031); pyroxofop and its esters(for example propargyl ester); quinclorac; quinmerac; quinofop and itsester derivatives, quizalofop and quizalofop-P and their esterderivatives, for example quizalofop-ethyl; quizalofop-P-tefuryl and-ethyl; renriduron; rimsulfuron (DPX-E9636); S 275, i.e.2-[4-chloro-2-fluoro-5-(2-propynyloxy)phenyl]-4,5,6,7-tetrahydro-2H-indazole;seebumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, i.e.2-[[7-[2-chloro-4-(trifluoromethyl)phenoxy]-2-naphthalenyl]oxy]propanoicacid and its methyl ester; sulfentrazon (FMC-97285, F-6285); sulfazuron;sulfometuron-methyl; sulfosat (ICI-A0224); TCA; tebutam (GCP-5544);tebuthiuron; terbacil; terbucarb; terbuchlor; terbumeton;terbuthylazine; terbutryn; TFH 450, i.e.N,N-diethyl-3-[(2-ethyl-6-methylphenyl)sulfonyl]-1H-1,2,4-triazole-1-carboxamide;thenylchlor (NSK-850); thiazafluron; thizopyr (Mon-13200); thidiazimin(SN-124085); thifensulfuronmethyl; thiobencarb; tiocarbazil;tralkoxydim; triallate, triasulfuron; triazofenamide; tribenuron-methyl;triclopyr; tridiphane; trietazine; trifluralin; triflusulfuron andesters (for exampl methyl ester, DPX-66037); trimeturon; tsitodef;vernolate; WL 110547, i.e.5-phenoxy-1-[3-(trifluoromethyl)phenyl]-1H-tetrazole; UBH-509; D-489; LS82-556; KPP-300; NC-324; NC-330; KH-218; DPX-N8189; SC-0774; DOWCO-535;DK-8910; V-53482; PP-600; MBH-001; KIH-9201; ET-751; KIH-6127 andKIH-2023.

For application, the formulations which are in the customary commercialform are, where appropriate, diluted in a usual way, for example in thecase of wettable powders, emulsifiable concentrates, dispersions andwater-dispersible granules using water. Compositions in dust form, soiland distribution granules, and sprayable solutions, are not normallydiluted with further inert substances before application.

The required application rate of the compounds of the formula (A)according to the invention varies with the external conditions such astemperature, humidity, the nature of the herbicide used, etc. It can bevaried within wide limits, for example between 0.001 and 10.0 kg/ha ormore active substance, but is preferably between 0.005 and 5 kg/ha.

The following examples serve to illustrate the invention:

A. FORMULATION EXAMPLES

-   a) A dust composition is obtained by mixing 10 parts by weight of a    compound of the formula (B1) and/or (B2) or of an active substance    mixture consisting of a herbicidal active substance of the    formula (A) and of a safener of the formula (B1) and/or (B2) and 90    parts by weight of talc as inert substance and comminuting in a    crusher mill.-   b) A wettable powder which can easily be dispersed in water is    obtained by mixing 25 parts by weight of a compound of the formula    (B1) and/or (B2) or of an active substance mixture consisting of a    herbicidal active substance of the formula (A) and of a safener of    the formula (B1) and/or (B2), 64 parts by weight of    kaolin-containing quartz as inert substance, 10 parts by weight of    potassium ligninsulfonate and 1 part by weight of    oleoylmethyltaurine sodium salt as wetting agent and dispersant and    milling in a pinned disk mill.-   c) A dispersion concentrate which can easily be dispersed in water    is obtained by mixing 20 parts by weight of a compound of the    formula (B1) and/or (B2) or of an active substance mixture    consisting of a herbicidal active substance of the formula (A) and    of a safener of the formula (B1) and/or (B2), 6 parts by weight of    alkylphenol polyglycol ether (®Triton X 207), 3 parts by weight of    isotridecanol polyglycol ether (8 EO) and 71 parts by weight of    paraffinic mineral oil (boiling range, for example, about 255 to    above 277° C.) and milling in a ball mill to a fineness below 5    microns.-   d) An emulsifiable concentrate is obtained from 15 parts by weight    of a compound of the formula (B1) and/or (B2) or of an active    substance mixture consisting of a herbicidal active substance of the    formula (A) and of a safener of the formula (B1) and/or (B2), 75    parts by weight of cyclohexanone as solvent and 10 parts by weight    of ethoxylated nonylphenol as emulsifier.

e) Water-dispersible granules are obtained by mixing 75 parts by weightof a compound of the formula (B1) and/or (B2) or of an active substancemixture consisting of a herbicidal active substance of the formula (A)and of a safener of the formula (B1) and/or (B2), 10 parts by weightcalcium ligninsulfonate,  5 parts by weight sodium lauryl sulfate,  3parts by weight polyvinyl alcohol and  7 parts by weight kaolin

-    milling in a pinned disk mill and granulating the powder in a    fluidized bed by spraying on water as granulation liquid.

f) Water-dispersible granules are also obtained by homogenizing andprecomminuting 25 parts by weight of a compound of the formula (B1)and/or (B2) or of an active substance mixture consisting of a herbicidalactive substance of the formula (A) and of a safener of the formula (B1)and/or (B2),  5 parts by weight sodium 2,2′-dinaphthylmethane-6,6′-disulfonate,  2 parts by weight oleoylmethyltaurine sodium salt,  1parts by weight polyvinyl alcohol, 17 parts by weight calcium carbonateand 50 parts by weight water

-    in a colloid mill, subsequently milling in a bead mill, and    atomizing and drying the suspension obtained in this way in a    spraying tower using a single-component nozzle.

BIOLOGICAL EXAMPLES Example 1

Various crop plants are grown in plastic pots with a diameter of 9 cm ina glasshouse to the stated stage and then treated with the particularherbicide or with a mixture of the herbicide and the safener by thepost-emergence method. This entails the herbicide of the formula (A) andthe compounds of the formula (B) being applied in the form of aqueoussuspensions or emulsions with a water application rate which converts to300 l/ha. 4 weeks after the treatment, the plants are assessed visuallyfor every type of damage by the applied herbicides, taking particularaccount of the extent of persistent growth inhibition. The evaluationtakes place in percentages (scale from 0 to 100%) compared withuntreated controls.

The results of the tests show that various safeners according to theinvention make it possible selectively to use the herbicides in cropssuch as wheat, barley and corn without this having an adverse effect onthe herbicidal activity.

TABLE 1 Phytotoxicity of herbicide/safener combinations according to theinvention in cereals Dose Herbicide Safener [g AS/ha] Phytotoxicity TypeA Type B A + B Wheat Barley A1  — 20 50 80 — 10 25 50 B1-1 20 + 40 0 1510 + 20 0 0 B1-9 20 + 40 0 25 10 + 20 0 0 B1-6 20 + 40 0 20 10 + 20 0 0A2  — 20 60 80 — 10 20 40 B1-1 20 + 40 5 15 10 + 20 0 0 B1-9 20 + 40 1015 10 + 20 0 0 B1-6 10 + 20 0 5 A3  — 20 65 95 — 10 30 60 B1-1 20 + 4010 20 10 + 20 0 0 B1-9 20 + 40 15 25 10 + 20 0 0 B1-6 20 + 40 10 25 10 +20 0 0 A4  — 40 40 80 — 20 15 30 B1-1 40 + 80 0 15 20 + 40 0 0 B1-9 40 +80 0 10 20 + 40 0 0 B1-6 40 + 80 0 25 20 + 40 0 0 A5  — 40 20 50 — 20 525 B1-1 40 + 80 0 0 20 + 40 0 0 B1-9 40 + 80 0 0 20 + 40 0 0 B1-6 40 +80 0 5 20 + 40 0 0 A6  — 40 40 85 — 20 15 30 B1-1 40 + 80 0 20 20 + 40 00 B1-9 40 + 80 0 5 20 + 40 0 0 B1-6 40 + 80 0 20 20 + 40 0 0 A10 25 3055 12 25 15  6 15 5 B1-1 25 + 12 0 5 12 + 6 0 0  6 + 3 0 0 A11 25 45 4512 20 25  6 5 10 B1-1 25 + 12 5 10 12 + 6 0 0  6 + 3 0 0 B1-9 25 + 12 1015 12 + 6 0 5  6 + 3 0 0 A12 25 10 25 12 10 15  6 5 8 B1-1 25 + 12 0 512 + 6 0 0  6 + 3 0 0 Conditions: Application takes place at the initialstage of tillering of wheat and barley

TABLE 2 Herbicidal activity on grasses Dose Herbicide Safener [g AS/ha]% effect on Type A Type B A + B ALMY APSP AVFA POAN A5 — 40 100 100 100100 20 99 100 99 100 10 95 98 85 98 B1-9 40 + 80 100 100 100 100 20 + 4098 100 100 100 10 + 20 95 95 90 95 B1-1 40 + 80 100 100 100 100 20 + 40100 99 100 100 10 + 20 90 99 80 98 B1-6 40 + 80 100 100 100 100 20 + 40100 100 98 99 10 + 20 95 95 80 95 A6 — 40 100 100 100 100 20 100 100 90100 10 99 99 80 99 B1-9 40 + 80 100 100 100 100 20 + 40 100 100 95 10010 + 20 100 98 95 100 B1-1 40 + 80 100 100 100 100 20 + 40 100 100 95100 10 + 20 95 95 80 95 B1-6 40 + 80 100 100 100 100 20 + 40 100 100 90100 10 + 20 95 100 80 100 A10 — 25 100 99 90 100 12 100 97 85 99  6 9880 75 85 B1-1 25 + 12 100 100 95 100 12 + 6 99 98 85 100  6 + 3 97 85 7590 A11 — 25 100 100 95 100 12 98 95 90 100  6 95 85 70 90 B1-1 25 + 12100 100 95 100 12 + 6 99 98 92 100  6 + 3 93 88 75 93 B1-9 25 + 12 100100 98 100 12 + 6 98 97 92 100  6 + 3 93 90 75 95 A12 25 99 98 90 99 1298 95 85 92  6 95 85 75 85 B1-1 25 + 12 100 100 95 100 12 + 6 97 99 8590  6 + 3 96 90 70 85 Stage of the grasses on application: 4-leaf stage

TABLE 3 Effect and selectivity in corn Phytotoxicity or Herbicide A Doseherbicidal effect in % (+ safener B) [g AS/ha] Corn AVFA ECCG SOHA A7100 60 100 90 95  50 40 100 80 90  25 25 100 60 90 A7 + B1-9 100 + 10015 100 95 100  50 + 50 0 100 80 95  25 + 25 0 100 60 90 A7 + B1-11 100 +100 10 100 90 100  50 + 50 0 100 90 90  25 + 25 0 100 60 80 A7 + B1-10100 + 100 10 100 90 90  50 + 50 0 100 90 90  25 + 25 0 100 70 80 A8 +B1-9 100 25 — — —  50 10 100 100 98  25 0 95 98 95 A8 + B1-9 100 + 50 0— — —  50 + 25 0 100 100 100  25 + 12 0 97 99 95 A8 + B1-11 100 + 50 0 —— —  50 + 25 0 — 100 100  25 + 12 0 — 98 95 A9 100 35 — — —  50 15 — 100100  25 0 — 99 98 A9 + B1-9 100 + 50 10 — — —  50 + 25 0 — 100 100  25 +12 0 — 99 95 A9 + B1-11 100 + 50 10 — — —  50 + 25 0 — 99 99  25 + 12 0— 95 98 A13 100 30 — — —  50 20 95 100 97  25 10 90 99 90 A13 + B1-9100 + 50 5 — — —  50 + 25 0 98 100 98  25 + 12 0 90 100 90 Stage: Corn -4 leaves AVFA - 3 leaves ECCG: start of tillering (i.e. 4 to 5 leaves)SOHA: 3 leavesAbbreviations in Tables 1 to 3:

-   g AS/ha=Application rate in grams of active substance per hectare-   ALMY=Alopecurus myosuroides-   APSP=Apera spica-venti-   AVFA=Avena fatua-   POAN=Poa annua-   ECCG=Echinochloa crus-galli-   SOHA=Sorghum halepense    (Continuation of Abbreviations in Tables 1 to 3)-   A1=N-(4,6-Dimethoxypyrimidin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-acetylaminobenzenesulfonamide-   A2=N-(4,6-Dimethoxypyrimidin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-(N-formyl-N-methylamino-methyl)benzenesulfonamide    sodium salt-   A3=N-(4,6-Dimethoxypyrimidin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-acetylaminobenzenesulfonamide    sodium salt-   A4=N-(4,6-Dimethoxypyrimidin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-(N-methyl-N-propionylamino)-benzenesulfonamide    sodium salt-   A5=N-(4,6-Dimethoxypyrimidin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-(N-isopropionylmethylamino)-benzenesulfonamide    sodium salt-   A6=N-(4,6-Dimethoxypyrimidin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-(N-methoxycarbonylaminomethyl)benzenesulfonamide    sodium salt-   A7=N-(4,6-Dimethoxypyrimidin-2-ylaminocarbonyl)-2-(N,N-dimethylaminocarbonyl)-5-(N-methoxycarbonylamino)benzenesulfonamide    sodium salt-   A8=N-(4,6-Dimethoxypyrimidin-2-ylaminocarbonyl)-2-(N,N-dimethylaminocarbonyl)-5-(N-formylamino)-benzenesulfonamide-   A9=N-(4,6-Dimethoxypyrimidin-2-ylaminocarbonyl)-2-(N,N-dimethylaminocarbonyl)-5-(N-propionylamino)benzenesulfonamide    sodium salt-   A10=N-(4,6-Dimethoxypyrimidin-2-ylaminocarbonyl)-2-(methoxycarbonyl-5-(N-methylsulfonylaminomethyl)benzenesulfonamide    sodium salt-   A11=N-(4,6-Dimethoxypyrimidin-2-ylaminocarbonyl)-2-(methoxycarbonyl-5-(N-methoxycarbonylaminomethyl)benzenesulfonamide    sodium salt-   A12=N-(4,6-Dimethoxypyrimidin-2-ylaminocarbonyl)-2-(methoxycarbonyl-5-(N-methylsulfonyl-N-methyl-aminomethyl)benzenesulfonamide-   A13=N-(4,6-Dimethoxypyrimidin-2-ylaminocarbonyl)-2-(N,N-dimethylaminocarbonyl)-5-(N-methoxycarbonylamino)benzenesulfonamide-   B1-1=Ethyl    1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate-   B1-6=Ethyl    1-(2,4-dichlorophenyl)-5-(trichloromethyl-(1H)-1,2,4-triazole-3-carboxylate-   B1-9=Ethyl 5,5-diphenyl-2-isoxazoline-3-carboxylate-   B1-10=n-Propyl 5,5-diphenyl-2-isoxazoline-3-carboxylate-   B1-11=Ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate

1. A herbicide/safener combination which comprises: A) at least oneherbicidal active substance or a salt thereof, which is a substitutedphenylsulfonylurea of the formula (A)

 in which W is O, A is —CH₂—, Q is O, or NR⁶, m is 0 or 1, n is 0, 1, 2or 3, R¹ is H, unsubstituted or substituted (C₁–C₆)alkyl, unsubstitutedor substituted (C₂–C₆)alkenyl, unsubstituted or substituted(C₁–C₆)alkynyl, or unsubstituted or substituted (C₃–C₆)cycloalkyl, R² isH, OH, (C₁–C₆)alkyl, (C₂–C₆)alkenyl, (C₂–C₆)alkynyl, (C₁–C₆)alkoxy,(C₂–C₆)alkenyloxy, (C₂–C₆)alkylnyloxy, (C₃–C₇)cycloalkyl, or(C₃–C₇)cycloalkoxy, R³ is —C(O)—R¹¹ or —S(O₂)—R²¹, R⁴ is halogen, CN,NO₂, (C₁–C₄)alkyl, (C₁–C₄)-alkoxy, [(C₁–C₄)alkyl]carbonyl,[(C₁–C₄)alkoxy]carbonyl, each of the four last-mentioned radicals beingunsubstituted or substituted, R⁵ is H, (C₁–C₅)alkyl or (C₁–C₄)alkoxy, R⁶is H, (C₁–C₄)alkyl, (C₃–C₄)alkenyl, (C₃–C₄)alkynyl, each of the threelast-mentioned radicals being unsubstituted or substituted by one ormore radicals from the group consisting of halogen, (C₁–C₄)alkyl,(C₁–C₄)alkoxy and (C₁–C₄)alkylthio, or is (C₁–C₄)alkoxy or OH, X¹, X²are, independently of one another, H, halogen, (C₁–C₆)alkyl,(C₂–C₆)alkenyl, (C₂–C₆)alkynyl, (C₃–C₇)cycloalkyl, (C₁–C₆)alkoxy,(C₂–C₆)alkenyloxy, (C₂–C₆)alkynyloxy, (C₁–C₆)alkylthio, mono- ordi-[(C₁–C₄)alkyl]-amino, each of the ten last-mentioned radicals beingunsubstituted or substituted by one or more radicals from the groupconsisting of halogen, (C₁–C₄)alkoxy, (C₁–C₄)haloalkoxy and(C₁–C₄)alkylthio, Z is CH, R¹¹ is H, (C₁–C₆)alkyl, (C₂–C₆)alkenyl, or(C₂–C₆)alkynyl, and R²¹ is (C₁–C₆)alkyl, (C₂–C₆)alkenyl or(C₂–C₆)alkynyl; and B) which is at least one safener from the group ofcompounds of the formulae (B1)

 in which X′ is hydrogen, halogen, (C₁–C₄)alkyl, (C₁–C₄)alkoxy, nitro or(C₁–C₄)haloalkyl, Z′ is OR⁷, SR⁷ or NR⁷R⁸ or is a saturated orunsaturated 3- to 7-membered heterocycle which has at least one nitrogenatom and up to 3 hetero atoms, is linked via the nitrogen atom to thecarbonyl group in (B1) and is unsubstituted or substituted by radicalsfrom the group consisting of (C₁–C₄)alkyl, optionally substitutedphenyl, R⁷ is hydrogen or an unsubstituted or substituted aliphatichydrocarbon radical, R⁸ is hydrogen, (C₁–C₆)alkyl, (C₁–C₆)alkoxy oroptionally substituted phenyl, n′ is an integer from 1 to 5, W′ has theformula:

or ethyl 5,5-diphenyl-2-isoxazoline-3-carboxylate (B1-9).
 2. Aherbicide/safener combination as claimed in claim 1, which is formulatedin the form of a composition (herbicidal composition) and contains 0.1to 95% by weight of active substances (A) and (B) and 1 to 99.9% byweight of customary formulating agents.
 3. A herbicide/safenercombination as claimed in claim 1, which contains the active substancesA and B in the ratio of from 1:100 to 100:1 by weight.
 4. A method forprotecting crop plants from phytotoxic side effects of herbicides A),which comprises applying an effective amount of safener B) before, afteror at the same time as herbicide A to the plants, plant parts, plantseeds or the growing area, where the combination of herbicide A) andsafener B) is as defined in claim
 1. 5. The method as claimed in claim4, wherein the crop plants are cereal plants, rice plants or cornplants.
 6. The method as claimed in claim 4, wherein the herbicides Aare applied at an application rate of 0.001 to 10 kg/ha active substanceand a safener:herbicide ratio by weight of from 1:100 to 100:1.
 7. Theherbicide/safener combination as claimed in claim 1, wherein theherbicide is selected from the group consisting ofN-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-(N-isopropionylmethylamino)-benzenesulfonamidesodium salt (A5);N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-(N-methoxycarbonylamino-methyl)benzenesulfonamidesodium salt (A6);N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-(N,N-dimethylaminocarbonyl)-5-(N-methoxycarbonylamino)benzenesulfonamidesodium salt (A7);N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-(N,N-dimethylaminocarbonyl)-5-(N-formylamino)-benzenesulfonamide(A8);N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-(N,N-dimethylaminocarbonyl)-5-(N-propionylamino)-benzenesulfonamidesodium salt (A9);N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-(methoxycarbonyl-5-(N-methylsulfonylaminomethyl)benzenesulfonamidesodium salt (A10); andN-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-(N,N-dimethylaminocarbonyl)-5-(N-methoxycarbonylamino)benzenesulfonamide(A13); and the safener is selected from the group consisting of ethyl1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate(B1-1) and ethyl 5,5-diphenyl-2-isoxazoline-3-carboxylate (B1-9).
 8. Aherbicide/safener combination as claimed in claim 7, wherein theherbicide is selected from the group consisting ofN-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-(N,N-dimethylaminocarbonyl)-5-(N-formylamino)-benzenesulfonamide(A8) andN-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-(methoxycarbonyl-5-(N-methylsulfonylaminomethyl)benzenesulfonamidesodium salt (A10); and the safener is selected from the group consistingof ethyl1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate(B1-1) and ethyl 5,5-diphenyl-2-isoxazoline-3-carboxylate (B1-9).
 9. Aherbicide/safener combination as claimed in claim 7, wherein theherbicide isN-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-(N-isopropionylmethylamino)-benzenesulfonamidesodium salt (A5) and the safener is ethyl1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate(B1-1).
 10. A herbicide/safener combination as claimed in claim 7,wherein the herbicide isN-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-(N-methoxycarbonylamino-methyl)benzenesulfonamidesodium salt (A6) and the safener is ethyl1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate(B1-1).
 11. A herbicide/safener combination as claimed in claim 7,wherein the herbicide isN-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-(N,N-dimethylaminocarbonyl)-5-(N-methoxycarbonylamino)benzenesulfonamidesodium salt (A7) and the safener is ethyl5,5-diphenyl-2-isoxazoline-3-carboxylate (B1-9).
 12. A herbicide/safenercombination as claimed in claim 7, wherein the herbicide isN-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-(N,N-dimethylaminocarbonyl)-5-(N-propionylamino)-benzenesulfonamidesodium salt (A9) and the safener is ethyl5,5-diphenyl-2-isoxazoline-3-carboxylate (B1-9).
 13. A herbicide/safenercombination as claimed in claim 7, wherein the herbicide is n-propyl5,5-diphenyl-2-N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-(N,N-dimethylaminocarbonyl)-5-(N-methoxycarbonylamino)benzenesulfonamide(A13) and the safener is ethyl 5,5-diphenyl-2-isoxazoline-3-carboxylate(B1-9).
 14. A herbicide/safener combination as claimed in claim 1,wherein W is O, A is —CH₂—, Q is 0, m is 0 or 1, n is O, R¹ is H orunsubstituted (C₁–C₆)alkyl, R² is H or (C₁–C₆)alkyl, R³ is —C(O)—R¹¹, R⁵is H or (C₁–C₅)alkyl, X¹, X²are, independently of one another, H,halogen, (C₁–C₆)alkyl, or (C₁–C₆)alkoxy, Z is CH; and R¹¹ is H or(C₁–C₆)alkyl.
 15. A herbicide/safener combination as claimed in claim 1,wherein, in the formula (B1), R⁷ is hydrogen, (C₁–C₁₈)alkyl,(C₃–C₁₂)cycloalkyl, (C₂–C₈)alkenyl or (C₂–C₈)alkynyl, where the aboveC-containing radicals are unsubstituted or substituted one or moretimes, by identical or different radicals from the group consisting ofhalogen, hydroxyl, (C₁–C₈)alkoxy, (C₁–C₈)alkylmercapto,(C₂–C₈)alkenylmercapto, (C₂–C₈)alkynylmercapto, (C₂–C₈)alkenyloxy,(C₂–C₈)alkynyloxy, (C₃–C₇)cycloalkyl, (C₃–C₇)cycloalkoxy, cyano, mono-and di-(C₁–C₄-alkyl)amino, carboxyl, (C₁–C₈)alkoxycarbonyl,(C₂–C₈)alkenyloxycarbonyl, (C₁–C₈)alkyl mercaptocarbonyl,(C₂–C₈)alkynyloxycarbonyl, (C₁–C₈)alkylcarbonyl, (C₂–C₈)alkenylcarbonyl,(C₂–C₈)alkynylcarbonyl, 1-(hydroxyimino)-(C₁–C₆)alkyl,1-[(C₁–C₄)alkylimino]-(C₁–C₄)alkyl, 1-[(C₁–C₄)alkoxyimino]-(C₁–C₆)alkyl,(C₁–C₈)alkylcarbonylamino, (C₂–C₈)alkenylcarbonylamino,(C₂–C₈)alkynylcarbonylamino, aminocarbonyl, (C₁–C₈)alkylaminocarbonyl,di-(C₁–C₆)alkylaminocarbonyl, (C₂–C₆)alkenylaminocarbonyl,(C₂–C₆)alkynylaminocarbonyl, (C₁–C₈)alkoxycarbonylamino,(C₁–C₈)alkylaminocarbonylamino, (C₁–C₆)alkylcarbonyloxy, which isunsubstituted or substituted by halogen, nitro, (C₁–C₄)alkoxy oroptionally substituted phenyl, or is (C₂–C₆)alkenylcarbonyloxy,(C₂–C₆)alkynylcarbonyloxy, (C₁–C₈)alkylsulfonyl, phenyl,phenyl-(C₁–C₆)alkoxy, phenyl-(C₁–C₆)alkoxycarbonyl, phenoxy,phenoxy-(C₁–C₆)alkoxy, phenoxy-(C₁–C₆)alkoxycarbonyl, phenylcarbonyloxy,phenylcarbonylamino, phenyl-(C₁–C₆)alkylcarbonylamino, where the 9last-mentioned radicals are unsubstituted or substituted one or moretimes, in the phenyl ring by identical or different radicals from thegroup consisting of halogen, (C₁–C₄)alkyl, (C₁–C₄)alkoxy,(C₁–C₄)haloalkyl, (C₁–C₄)haloalkoxy and nitro, and radicals of theformulae —SiR′₃, —O—SiR′₃, R′₃Si—(C₁–C₈)alkoxy, —CO—O—NR′₂, —O—N═CR′₂,—N═CR′₂, —NR′₂, —O—NR′₂, —CH(OR′)₂, —O—(CH₂)_(x)—CH(OR′)₂, —CR′″(OR′)₂and —O—(CH₂)_(x)—CR′″(OR″)₂, in which the R′ in the said formulae are,independently of one another, hydrogen, (C₁–C₄)alkyl, phenyl which isunsubstituted or substituted one or more times by identical or differentradicals from the group consisting of halogen, (C₁–C₄)alkyl,(C₁–C₄)alkoxy, (C₁–C₄)haloalkyl, (C₁–C₄)haloalkoxy and nitro, orpairwise are a (C₂–C₆)alkanediyl chain and x=0 to 6, and R″ is hydrogenor (C₁–C₄)alkyl, and a substituted alkoxy radical of the formulaR″OCHR′″CH(OR″)—(C₁–C₆)alkoxy, in which the R″ are, independently of oneanother, (C₁–C₄)alkyl or together are (C₁–C₆)alkanediyl and R′″ ishydrogen or (C₁–C₄)alkyl, W′ has the formula:

R⁹is hydrogen, (C₁–C₈)alkyl, (C₁–C₈)haloalkyl, (C₃–C₁₂)cycloalkyl oroptionally substituted phenyl, R¹⁰ is hydrogen, (C₁–C₈)alkyl,(C₁–C₈)haloalkyl, (C₁–C₄)alkoxy-(C₁–C₄)alkyl, (C₁–C₆)hydroxy-alkyl,(C₃–C₁₂)cycloalkyl or tri-(C₁–C₄)alkyl-silyl.
 16. A herbicide/safenercombination as claimed in claim 1, wherein, in formula (A), R¹ is(C₁–C₆)alkyl, (C₂–C₆)alkenyl, (C₂–C₆)alkynyl, (C₃–C₆)cycloalkyl each ofthe four last-mentioned radicals being unsubstituted or substituted byone or more radicals from the group consisting of halogen, CN,(C₁–C₄)alkoxy, (C₁–C₄)alkylthio, (C₁–C₄)haloalkoxy,mono-(C₁–C₄-alkyl)amino, di-(C₁–C₄-alkyl)amino, (C₁–C₄)alkylsulfonyl,(C₁–C₄-alkyl)aminocarbonyl, di-(C₁–C₄-alkyl)aminocarbonyl, phenyl andsubstituted phenyl, and R² is H, OH, (C₁–C₆)alkyl, (C₃–C₇)cycloalkyl,(C₂–C₆)alkenyl, (C₂–C₆)alkynyl, (C₁–C₆)alkoxy, (C₃–C₇)cycloalkoxy,(C₂–C₆)alkenyloxy, (C₂–C₆)alkynyloxy, the eight last-mentioned radicalsbeing unsubstituted or substituted by one or more radicals from thegroup consisting of (C₁–C₄)alkoxy, (C₁–C₄) haloalkoxy,(C₂–C₄)alkenyloxy, (C₂–C₄)haloalkenyloxy, (C₂–C₄)alkynyloxy, (C₂–C₄)haloalkynyloxy, (C₁–C₄)alkylthio, (C₁–C₄)haloalkylthio, halogen, OH,NH₂, mono- and di-[(C₁–C₄)alkyl]amino, CN, NO₂, CONH₂, CHO,[(C₁–C₆)alkyl]carbonyl, (C₁–C₄)alkylsulfonyl, [(C₁–C₄)alkoxy]carbonyl,mono- and di-[(C₁–C₄)alkyl]aminocarbonyl, and in the case of cyclicradicals also (C₁–C₄)alkyl and (C₁–C₄)haloalkyl.
 17. A herbicide/safenercombination as claimed in claim 1, wherein R¹ is (C₁–C₆)alkyl,(C₂–C₆)alkenyl, (C₂–C₆)alkynyl, (C₃–C₆)cycloalkyl, each of the fourlast-mentioned radicals being unsubstituted or substituted by one ormore radicals selected from the group consisting of F, Cl, Br, I, CN,OCH₃, OCF₃, N(CH₃)₂, SO₂CH₃, CO₂CH₃, CO₂N(CH₃)₂ and phenyl, R² is H,(C₁–C₄)alkyl, (C₂–C₄)alkenyl, (C₂–C₄)alkynyl, (C₃–C₆)cycloalkyl or(C₁–C₄)haloalkyl.